Reversible emulsion and application therefor



mama Apr. 35,1944

w ns navna'smnn nnnmsrou sun armresrrou n a James H. ri-uz, swim; and Edwin L. abunson, Ghatham, N. 1., assignors to National Oil lroductscompanyJlai-rlso tion of New Jersey lilo Drawing.

Application January Serial No. 425,856

n. N. 1.. a corpora This invention relates to, emulsions of waterin-oil, oil-in-water and intermediate types, and

more particularly'to such emulsions which are stablized by means of cationic surface active amino compounds.

. Heretofore emulsions of water in oil have been prepared which are convertible by dilution and vigorous agitation to emulsions of oil in water, However, it has not been possible to prepare emulsions of water in oil which are stable at or near the inversion point or which may be converted by very mild agitation and dilution to oilin-water emulsions, notwithstanding the considerable'need for such stable and readily invertible emulsions.

Accordingly, it is an object of this invention to provide water-in-oil emulsions which can be readily and smoothly inverted and which will be stable at or near the inversion point.

Another object is to provide a water-in-oil emulsion which can' be added to a batch or stream of aqueous stock in process to obtain the effect of adding an oil, without, however, encountering any subsequent difiiculties due to separation of the oil from the stock.

A further object is to provide an agent and process for defoaming aqueous stock which will require only a minimum quantity of material and 'which will not interfere with any subsequent operations upon the stock.

The above and other objects are secured by this invention in an emulsion of an oily material, such as a petroleum oil and water, stabilized by a cationic surfaeeactivefatty amino compound,

such as the amide produced by reacting oleic acid with diethylene triamine, which compound is adjusted by means of a weak acid, such as acetic acid, to a pH of 6 or below. At moderate concentration of the oil, the oil will be the continuous phase,but upon dilution with water the emulsion inverts to'become an oil-in-water emulsion. Both the undiluted and diluted emulsions areentirely stable at any point in the process of inversion, which will take place without the rial eventually disperse throughout the stock without separating. Specifically, it is often desired to break the foam on the surface of Paper stock, glue, starch, casein solutions undergoing .ill

. with ethanol ethylene diamine, etc.

use of these emulsions for many applications, as V where it is desired to treat an aqueous stock with an oily material and to have the oily mateenzymatic and hydrolytic processes and the like, by adding an oily material threto. The emulsions of this invention will act as such an oil. but will eventually disperse smoothly and com- -pletely throughout thebody of the stock and thus avoid interference with any subsequent operations. 7

The amide of oleic acid with ethylene diamine was cited as a suitable emulsifying agent for the practice of this invention, but any fatty compound having at one end a fatty residue of 10 or more carbon atoms and no hydrophilic groups, and presenting at the other extremity an amine group, will be suitable. Examples of such compounds are fatty amines and the amides of the fatty acids with the'polyamines. As an acid residue'in such an amide there may be cited oleic acid, lauric acid, myristic acid, palmitic acid, stearlc acid, palmitoleic acid,'arachidic acid and the like. Instead ofthe pure acids the fatty acid residues contained in fats and oils, such as coconut oil, soyabean oil, lard, tallow, peanut oil, corn oil, hydrogenated soyabean oil, hydrogenated fish oil, and the like may be employed. The amide residue may be derived from an? polyamine such as ethylene diamine, diet-hylene triamine, ethanol ethylene diamine, tetraethylene pentamine, 1,3 diamino isopropanol and the like. Specific amides coming within the above requirements are exemplified in the amide produced by reacting oleic acid and ethylene diamine; rice oil with diethylene triamine; soyabean oil with diethylene triamine, hydrogenated soyabean oil Examples of suitable amines are stearyl amine, oleyl amine, lauryl amine, dilauryl amine, and the like.

Acetic acid was cited as a suitable acid for adjusting the pH of the cationic surface active amino compound. However, any acid may be used for this purpose, preferably a weak acid, in order that the pH may be adjusted more accurately and that a buffering action may be secured. A suiiicient amount of the acid is employed to reduce the pH ofthe amino compound to 6 or below when the amino compound is in 2% aqueous solution.

Petroleum oil was cited as an oil suitable -for theoily phase of emulsions according to this invention. However, any mineral, vegetable or animal oil, fat or wax, the viscosity of which is not too great to interfere with the inversion of the phases, may be employed. Mineral oils may vary in viscosity from about 35 seconds to 300 seconds Saybolt (100 F.) Suitable oils, other than mineral oils, are exemplified in soyabean oil, cottonseed oil, rice oil, peanut oil. corn oil, teaseed oil, neats-foot oil, cod oil, castor oil, whale.

immediately.

. to an oil-inwater emulsion as the'emulsion in taining mostly oil, which emulsion may be converted at the point of use into an oil-in-water.

emulsion without diiliculty or special equipment.

Further, the diluted and inverted emulsions have the propertiesunlike those'of most oil-in-water emulsions, in that they have a greasy feel and a tendency to prevent and destroy foam on any aqueous bodies containing them. Further, when these emulsions are added to any batch or stream of materials in" process, they will exert the same action as an unemulsified oil would, with the advantages that-a considerably less amount of actual oil is used, since the bulk of the emulsion will be constituted of water, and further, that the emulsion will subsequently disperse complete ly in the stock without separating and interfering at subsequent points in the process. For instance, the emulsions may be added to paper or glue stocks at.any point where foaming is encountered and will kill the foam at that point. However, the oil will eventually becom distributed thoroughly throughout the body of the stock and will not cause troubles such as, in the case of the paper, streaks in the paper web made therefrom, or in the case of glue, fish eyes on the coatings made therefrom. Further, these emulsions will not readily attack the rubber or other oil-sensitive materials contacted by the stock to which they are added.

For a fuller understanding of the nature and objects of the invention, reference should be had to the following examples which are given merely to further illustrate the invention, and are not'to be construed in a limiting sense, all parts given being by weight.

Example I 270 parts of #2 fuel oil, parts of the monoamide produced by reacting oleic acid with ethylene diamine, and 1 part of glacial acetic acid were mixed. 300 parts of water were added and mixed in with agitation to form. an emulsion of .water in oil. 200 additional parts of water were without breaking.

An emulsion of water in oil prepared as just described, but without having been diluted with water, was added to a stream of paper stock going to the vat of a cylinder machine, in which foaming was giving trouble.

" Example 11 270 parts of #2 fuel oil, 80 parts of the monoamide produced by the reaction of hydrogenated soyabean oil with ethanolethylene diamine, and 1 part of gracial acetic acid were mixed. 300 parts of water were added and mixed in with agitation to form an emulsion of water in oil. This emulsion exhibited the same capability of inversion The foam broke down Example I. The emulsion of this example had excellent defoaming properties.

Example III 30 parts of the monoamides formed by react.- ing a mixture of rice oil and cottonseed oil with diethylene triamine were substituted for the 'monoamides employed in the procedures of .Ex-

amples I and II. The resulting water-in-oil emulsions exhibited the same properties of ready inversion and of foam prevention as did the emulsions in Examples I and II.

Example IV The procedures of Examples I and II were repeated, using stearylamine in place of the mono sions which are readily inverted by mere dilu- 'tion and slight agitation. When such inversion occurs as the emulsions are added to aqueous,

stock, novel surface effects are obtained, similar to effects obtained by the use of unemulsifled oils. but without the difiiculties attending th use of unemulsifled oils. 4

Having described our invention, what we claim as new and desire to secure by. Letters Patent is:

'1. A reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly a cationic surface acitve fatty amino compound, the fatty residue of which contains at least 10 carbonatoms and no hydrophilic groups, the amino compound being adjusted with acid to have a pH of about 6.0 cries in 2% aqueous solution.

2. A reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly the monoamide formed by reacting oleic acid and ethylene diamine, the monoamide being adjusted with acid to have a pH ofabout 6.0 or less in 2%. aqueous solution. v

3. A reversible emulsion of water in oil, the

active emulsifying ingredient of which comprises chiefly the monoamide formed by reacting hydrog'e'nated soyabean oil with ethanol ethylene diamine, the monoamide being adjusted with acid to have a pH of about 6.0 or less in. 2% aqueous solution. I

4. A reversible emulsion of'water in oil, the active emulsifying ingredient of which comprises chiefly a fatty amine, the fatty residue of which contains at least 10 carbon atoms and no hydrophilic groups, the amine being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution. I

5.'A reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly stearylamine, the stearylamine being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.

chiefly a cationic surface active fatty amino com-.

pound, the fatty residue of which contains at least carbon atoms and no hydrophilic groups,

the amino compound .being adjusted by means of acetic acid to have a pH of in 2% aqueous solution. l

7. A reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly a cationic surface active fatty amidoamine, the fatty residue of which contains at least 10 carbon atoms and no hydrophilic groups, the amido-amine being adjusted by means of acetic acid to have apH of about 6.0 or less in 2% aqueous solution.

8. A reversible emulsion of w ater in oil, the active emulsifying ingredient of which comprises about 6.0 or less chiefly the monoamide formed by reacting oleic,

acid and ethylene diamine, the monoamide being acfiusted by means of acetic acid to have 'a pH of about 6.0 or less in 2% aqueous solution.

9. A reversible emulsion of water in oil, the' active emulsifying ingredient of which comprises chiefly a fatty amine, the fatty residue of which contains at least 10 carbon atoms and no hydrophilic groups, the amine being adjusted by means of acetic acid to have a pH of about 6.0 or less in 2% aqueous solution.

10. A defoaming agent comprising oil, water and an emulsifying agent which compriseschiefly.

a cationic surface active fatty amide-amine, the

fatty residue of which contains at least. 10 carbon atoms and no hydrophilic groups, the amidoamine being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.

11. Method of suppressing foam in aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly a cationic surface active fatty amino compound,

the fattyresidue of which contains at least 10 carbon atoms and no hydrophilic groups, the amino compound being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.

12. Method of suppressing foam in aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly a cationic surface active fatty amide-amine, the fatty residue of which contains at least 10 carbon atoms and no hydrophilic groups, the amido amine compound being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.

13. Method of suppressing foam in aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly the monoamide formed by reacting hydrogenated soyabean oil with ethanol ethylene diamine, the amide being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.

14. Method of suppressing foam in aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly 15. Method of suppressing foamin aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly stearylamine, the stearylamine being adjusted with acid to have a. pH of about 6.0 or less in 2% aqueous solution, I JAMES H. FRITZ.

EDWIN A. ROBINSOLL. 

